Production of anilin black on fibers and fabrics.



ARTHUR GEORGE GREEN, OF LEEDS, ENGLAND.

PRODUCTION OF ANILIN BLACK (3N FIBERS AND FABRICS.

sees-is.

31o Brewing.

Specification of Letters Patent.

Application filed January 15, 1908. Serial No. 410,934.

Patented May 31, 195149.

To all whom it may concern."

Be it known that I, ARTHUR GEORGE GREEN, of The University, Leeds, Yorkshire, England, consulting chemist, have invented certain new and useful Improvements Relating to the Production of Anilin Black upon Fibers and Fabrics, of which the following is a specification.

In the ordinary method of producing an aged or oxidation black upon textile fibers or fabrics, the material is padded or printed with a solution containing a salt of anilin, usually the hydrochlorid, together with an oxidizing agent, usually sodium or potassium chlorate, and an oxygen carrier,

usually a salt of copper or vanadium. Upon thematerial thus prepared the black is then developed by hanging in a Warm chamber more or less saturated with, moisture (aged). In order to further complete the oxidation, the material is frequently subjected to a final treatment With a hot solution. of a bichromate chromed). In applying this process to cotton fabrics, great care is required in order to prevent the weakening or tendering of the cotton fiber. The conditions as to humidity and temperature of the aging chamber, the duration of agin and other circumstance so have to be care ally and exactly controlled, and even with the exercise of all possible precautions a certain weakening of the ma terial can scarcely be avoided. The cause of this weakening is two-fold: the oxidi-7. $5 ing action exerted bythe oxits of chlorin produced from the chlorate, which tend to convert the cotton into oxycellulose; (ii). the destructive action of the hydrochloric acid or other mineral acid set free from its combination with anilin.

The present invention relates to a new and improved method of producing anjilin black, which is not attended by the above disadvantages, and in which all weakening or,

5 tendering of the cotton fiber may be avoided Without the exercise of any extreme care. At the same time a fuller utilization of the anilin is rendered possible, the danger ol. fire from spontaneous inflammation is removed, the risk of injury to the health of the workpcople greatly diminished, the manufacture is simplified and greater speed of pl'fidlliitldil is attainable. The process may also be applied in cases in which prolonged steaming is necessary, as for instance in printing together with tannin colors. It is also applicable to the dyeing and printing of linen, ramie, or silk, or of mixtures of these fibers with one another or with cotton.

The new process is characterized and dis tinguished from all other known processes of producing anilin black, by the fact that it does not require the presence of an oxidizing agent in the padding or printing mixture, the oxidation of the anilin to the aged condition known as emeraldin or to nigranilin being effected solely or mainly by the oxygen of the air. The possibility of dispensing with an oxidizing agenhend thus of avoiding the tendering or weakening of the fiber due to oxycellulose formation, depends on the discovery that a small quantity of a paradiamin or of a para-amid0- phenol or other substance capable of'producmg an indamm by condensation with analin, it added to a mixture containing analin and a suitable oxygen carrier, such as a salt of copper, greatly accelerates the oxidation of the anilin by atmospheric oxygen. Further whereas in the ordinary processes of producing an aged black the quantity of min eral acid employed cannot be materially reduced below the proportion of one equivalent of the latter to one equivalent of base, under the new conditions here set forth a mixture which is basic may be used with satisfactory results for the purpose. Still further, the hydrochloric acid or other mineral acid may be wholly or in part replaced by an organic acid, such for instance as formic acid, without materially affecting the quality of the black obtained. In either 'asc, whether a basic mixture is employed or a mixture containing an organic acid, the tendering ot the tiberby free mineral acid liberated during aging or steaming is avoided. own when these operations are unusually prolonged. The action of the para diamin or para-amidophenol is believed to be a on t u lytic one, since the quantity employed need only be small in proportion to the and iin, and may be varied within Wide limits. 'lhose substances bring about the oxidation of the anil in by intermediate formation of complex indannns, from which they are constantly regenerated. in footy any other compound, such as a nitroso compound or quinone imid, capable of giving rise tomdamins under the conditions employed, may be used for the same purpose.

As suitable oxygen-carriers the chlorids of copper have been found to give the best results, and in order to prevent the premaure formatitm of oxidation-products in the padding or printing mixture, it has been found preferable to employ the copper in the form of a cuprou, salt. A convenient method of otter-ting this is to add to the mixture cupric (:hlorid or other cupric salt, together with a sultite in quantity sutlicicnt to reduce the cupric salt to the cuprous state, and a sullicieut amount of a soluble chlorid, such as soilium chlorid, potassium chlorid, or ammonium chlorid, to keep the cuprous chlorid in solution. Mixtures thus prepared are quite stable, and remain clear and colorless on exposure to air for a considerable period. Just as in the ordinary method of producing anilin black, so here also the analin may be replaced wholly or in part by its homologues such as orthotoluidin or mctaxylidin.

No claim is made to any process for the production of a black from a mixture of anilin and a paratiliamin in which the oxidation is e,tlected substantially by means of a chlorate.

The mixtures: composed as above are applied to texti r'j tibers and fabrics in the usual manner, namely, by padding or printin In the latter case the mixture is suitably thickened by means of any of the usual .JClitlllllg agents. Oxidation is then effected by exposure of the material to air, etl'cctcd either by passage through the ordi- .nary rapid ager, by hanging in a moist atmosphere, by steaming, or by any other convenient means. Finally it is washed and dried; or tlttnltlillg' to circumstances it may be subjected to a linal treatment with a bichromate either alone or in presence of other materials as at, present employed in the after-treatment of an aged anilin black, with the object of further oxidizing the emeraldin, 'or of rendering the black less liable to green.

Among the various paradiamins and paraamidophenols which are suitable for the purpose of this invention, the following may be specially mentioned li!X':l-|)lItll)'ltHutliilmiiL. lara-plienylone dianiin sult'o lara-pht-nyleuediumiu irbox Puru-tolylcnedtumin -11 lliethyl paiapltrn lenc diamin. i

and their analogues, homologues, or derivatives.

In place of para-diamins and para -amido phenols, there may be used any other sub stance which under the conditions employed will give rise to an indamin by condensation with anilin, such, for instance, as one of the follow1ngz-- Quinone mono-mild ,CH4 g Quinonc diimidi i v ..C H Rv% and their analogues, homologucs,or derivatires.

The following examples of suitable con positions for padding mixtures are given in order to illustrate the general method of carrying out this invention; the details may however be varied within wide limits as set forth above.

Example L-The padding mixture is repared by adding a solution composed of 4:8 parts of cupric chlorid, 110 parts of ammonium chlorid, and 14- parts of sodium metabisultite in 500 parts of cold Water, to a solution composed of 50 parts of anilin, 2 parts of paraphenylcnediamin,15 parts of hydrochloric acid (30 percent. HCl) and 15 parts of formic acid (90 per cent.) in 1,500 parts of cold water.

Example II.-'lhe padding mixtu e prepared by adding a solution composed of 48 parts of cupric ehlorid, 140 parts of ammonium chlorid, and 14: parts of sodium metabisultite in 500 parts of cold water, to a solution composed of 50 parts of anilin, 4tparts of pa raphenylenediamin, parts of formic acid (90 per cent.) in 1,500 parts of cold water.

Example i1l.--lhe padding mixture is prepared by adding a solution composed of 48 parts of cupric chlorid, H0 parts of ammonium ohlorid, and 1st parts of sodium metabisultite in 500 parts of cold Water, to a solution composed of 50 parts of anilin, 4 parts of paraphenylenediamin, and 50 parts of hydrochloric acid (30 per cent), in 1,500 parts of cold water.

What I claim and desire to secure by Let I ters Patent is 1. A process for the production of emeraldm and amlm black upon textlle fibers and fabrics, comprising oxidation of an anilin base substantially by atmospheric oxygen in fabrics. comprisinq oxidation of an aniiin base sol ins presence of a copper salt associated Wlilil pamphenylenediamin. v v

4:, A. p 'ocess for the production of emersidin :indanilin black upon textiie fibers and fabrics, comprising the application to the some of mixture containing an amlm 'base, in]. acid, a salt of cooper and $5111)- stance capable ofa-sproducing an indemin by condensation with alinin, and afterward subjecting the material to atmospheric oxidation'.

5. A. process for the production of emeraliiiii and. a'iiiiinbiack upontextile fibers and fabrics, comprising the application to the same oi ture containing an amino. ease, eniacici iii of copper and a paradmmin,

:stantiaily y atmospheric oxygen iii and" afterward subjecting the material toa tmospiierio oxiiiation.

6. A process for the production of emer diamin, and subsequent subjection of the material to atmospheric oxidation. in witness whereof, I have hereunto signed my name in the presence of two subscribing Witnesses.

ARTHUR GEORGE GREEN.

Wiii'iesses:

THOMAS LAING Wi-HTEHEAD, liosisc'r MILTON SPEAsPomT. 

